The present invention relates to a fragrance composition comprising a fragrance base and a lipophilic solubilizing agent based on at least one polyorganosiloxane containing a polar or polarizable function; the invention also relates to the use of polyorganosiloxanes containing a polar or polarizable function as agents for dissolving fragrance bases and emollients in fragrance compositions.
A first subject of the invention consists of a fragrance composition comprising a fragrance base and a lipophilic agent for dissolving the said fragrance base, the said solubilizing agent being based on at least one linear polyorganosiloxane containing a polar or polarizable function of formula (I)
(R1)(R2)(R3)Sixe2x80x94Oxe2x80x94[Si(R4)(Z)xe2x80x94O]nxe2x80x94[Si(R5)(R6)xe2x80x94O]mxe2x80x94Si(R7)(R8)(R9)xe2x80x83xe2x80x83(I)
or a cyclic polyorganosiloxane of formula (Ixe2x80x2) 
in which formula (I)
the symbols R1 and R9 are identical or different and represent the symbol Z or an alkyl radical containing from 1 to 8 carbon atoms, preferably 1 or 2 carbon atoms, most particularly 1 carbon atom
the symbols R2, R3, R4, R5, R6, R7 and R8 are identical or different and represent an alkyl radical containing from 1 to 8 carbon atoms, preferably 1 or 2 carbon atoms, most particularly 1 carbon atom
the symbol Z represents a polar or polarizable organic radical
n is an integer or decimal number which can range from 0 to 5, preferably equal to 0 or 1,
at least one of the radicals R1 and R9 representing the symbol Z when n is equal to 0
m is an integer or decimal number which can range from 0 to 5, preferably equal to 0
formula (Ixe2x80x2) in which
the symbols R4, R5, R6 and Z have the same definition as that given above
n is an integer or decimal number which can range from 1 to 5, preferably equal to 1
m is an integer or decimal number which can range from 1 to 5, with n+m at least equal to 3,
the said polyorganosiloxane having the following Hansen solubility parameters
xcex4D of London interactions ranging from 8 to 21 (J/cm3)xc2xd
xcex4P of Keesom interactions of greater than 0 and possibly ranging up to 25 (J/cm3)xc2xd
xcex4H of hydrogen bonding ranging from 0 to 23 (J/cm3)xc2xd.
The three-dimensional solubility space, in which the solvents and all the organic molecules exist, is defined by C M Hansen in xe2x80x9cThe three dimensional solubility parametersxe2x80x9d J. Paint Technol. 39, 105 (1967); xcex4D, xcex4P and xcex4H represent the partial solubility parameters associated, respectively, with the London dispersion forces, the Keesom polarity forces and the hydrogen bonding forces, given that these partial parameters are the components of the overall solubility parameter xcex4, referred to as the Hildebrand solubility parameter, associated with the voluminal cohesion of the molecule.
Examples of polar organic radicals Z which may be mentioned are
ester groups of formulae xe2x80x94Rxe2x80x2OOCxe2x80x94Rxe2x80x3 and xe2x80x94Rxe2x80x2xe2x80x94COORxe2x80x3xe2x80x2 directly linked to silicon, in which formulae
Rxe2x80x2 represents a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
Rxe2x80x3 represents a C1-C8, preferably C1-C3, alkyl group
Rxe2x80x3xe2x80x2 represents a C1-C5, preferably C1-C3, alkyl group
the hydroxyl or alcohol groups of formula xe2x80x94Rxe2x80x2xe2x80x94Oxe2x80x94(RO)xH directly linked to silicon, in which formula
Rxe2x80x2 represents a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
R represents a linear or branched alkylene group, which may be identical or different, containing 2 or 3 carbon atoms
x can range from 0 to 20
primary or secondary amido groups xe2x80x94Rxe2x80x2xe2x80x94COxe2x80x94NH(R), directly linked-to silicon, in which Rxe2x80x2 represents a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
carboxyl groups xe2x80x94Rxe2x80x2xe2x80x94COOH, directly linked to silicon, in which Rxe2x80x2 represents a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
linear or branched, saturated or unsaturated, C6-C20 haloaliphatic radicals, in particular chloro- or fluoroaliphatic radicals
saturated or unsaturated, C5-C6 halocycloaliphatic radicals, in particular chloro- or fluorocycloaliphatic radicals, directly linked to silicon via a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
aryl radicals, preferably C6 aryl radicals, substituted with at least one halogen atom (in particular chlorine or fluorine), directly linked to silicon via a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms.
Mention may be made more particularly of 3-propylol, 2-propyloxyethanol, diethyl 3-propyl malonate and ethylpyrrolidone radicals, which radicals can be obtained by opening the vinylic double bond of, respectively, allyl alcohol, allyloxyethanol, diethyl allyl malonate or vinylpyrrolidone, as well as 3-propylacetate.
Examples of polarizable organic radicals Z which may be mentioned are
linear or branched C6-C20 aliphatic radicals containing at least one internal ethylenic unsaturation, preferably two conjugated double bonds
ethylenically unsaturated C5-C6 cycloaliphatic radicals, optionally substituted with at least one C1-C8 alkyl group, linked directly to silicon via a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms
a phenyl radical
aryl radicals, preferably C6 aryl radicals, optionally substituted with at least one C1-C8 alkyl or C6 aryl group, linked directly to silicon via a saturated or unsaturated, linear or branched aliphatic multivalent group containing from 2 to 10 carbon atoms.
Mention may be made more particularly of a phenyl radical and the radicals obtained by opening the vinylic double bond of styrene, of xcex1-methylstyrene, of xcex1-methylstyrene dimer, of dihydromyrcene, of limonene, etc., or the terminal triple bond of phenylacetylene, etc.
The said radical Z is preferably a phenyl radical, a phenylalkyl radical in which the alkyl residue contains from 2 to 10 carbon atoms, or a phenylalkenyl radical in which the alkenyl residue contains from 2 to 10 carbon atoms, in particular phenyl(methyl)methyl, phenylethenyl and, most particularly, phenylethyl. Most preferably, the fragrance composition comprises a mixture of polyorganosiloxanes predominantly containing a polyorganosiloxane containing a phenylethyl radical, a smaller amount of a polyorganosiloxane containing a phenyl(methyl)methyl radical and a small amount of a polyorganosiloxane containing a phenylethenyl radical.
Preferably, the said polyorganosiloxane is a organodisiloxane MM of formula (I) in which n and m are equal to 0 and R1 and R9 represent a phenyl radical, in particular diphenyltetramethyldisiloxane, or a linear organotrisiloxane MDM of formula (I) in which n is equal to 1 and m is equal to 0, the symbols R1, R2, R3, R4, R7, R8 and R9 preferably being methyl radicals.
The said polyorganosiloxanes of formula (I) or (Ixe2x80x2) in which the polar or polarizable function (Z) is other than phenyl can be obtained in a known manner by hydrosilylation between at least one hydrogenopolyorganosiloxane of formula (II) or (IIxe2x80x2)
(R1)(R2)(R3)Sixe2x80x94Oxe2x80x94[Si(R4)(H)xe2x80x94O]nxe2x80x94[Si(R5)(R6)xe2x80x94O]mxe2x80x94Si(R7)(R8)(R9)xe2x80x83xe2x80x83(II)

in which formulae the symbols R1, R2, R3, R4, R5, R6, R7, R8, R9, n and m have the same definition as that given above,
and the compound containing vinylic or terminal acetylenic unsaturation from which the radical Z is derived, in the presence of a hydrosilylation catalyst, in particular such as platinum.
This operation can be carried out with a slight excess of one or other of the reagents, generally up to 10 mol % relative to the stoichiometry, at a temperature of about 50xc2x0 C. to 100xc2x0 C., preferably from about 50xc2x0 C. to 80xc2x0 C., in the presence of 5 to 50 parts by mass of platinum (for example Karstedt catalyst) per million parts by mass of monomers used.
The hydrogenopolyorganosiloxanes preferably used are hydrogenoheptaorganotrisiloxanes MDxe2x80x2M, particularly hydrogenoheptamethyltrisiloxane.
Among the compounds containing vinylic or terminal acetylenic unsaturation which can preferably be used, mention may be made of allyl alcohol, allyloxyethanol, diethyl allyl malonate, styrene, xcex1-methylstyrene, xcex1-methylstyrene dimer, dihydromyrcene, limonene, vinylpyrrolidone and phenylacetylene. The said compound is most preferably styrene.
One specific embodiment of the first subject of the invention consists of a fragrance composition comprising a fragrance base and a lipophilic agent for dissolving the said fragrance base, the said solubilizing agent being based on phenylethylheptamethyltrisiloxane in particular based on a mixture of heptamethyltrisiloxanes containing polymerizable functions consisting
for more than 70% by mass, generally for at least 75% by mass, of phenylethylheptamethyltrisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z1)xe2x80x94Oxe2x80x94SiMe3,
in which Z1 represents the xe2x80x94CH2xe2x80x94CH2xe2x80x94Ph function
for less than 25% by mass, generally from 10 to 20% by mass, of trisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z2)xe2x80x94Oxe2x80x94SiMe3, 
in which Z2 represents the xe2x80x94CH(CH3)xe2x80x94Ph function
and less than 5% by mass, generally from 0 to 2% by mass, of trisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z3)xe2x80x94Oxe2x80x94SiMe3,
in which Z3 represents the xe2x80x94CHxe2x95x90CHxe2x80x94Ph function
in which formulae Me represents a methyl radical and Ph represents a phenyl radical.
The said mixture can be obtained by hydrosilylation reaction at a temperature of from 50 to 150xc2x0 C., preferably from 50 to 100xc2x0 C., most particularly from 60 to 90xc2x0 C., of hydrogenoheptamethyltrisiloxane (reagent SiH) and of styrene (reagent Vi), in the presence of hexamethyldisiloxane as solvent. This hydrosilylation operation is carried out by simultaneously introducing the two reagents (Vi) and (SiH) into the reaction medium comprising the solvent and a hydrosilylation catalyst, this introduction being carried out such that the respective amounts of the two reagents (Vi) and (SiH) correspond to a reagent (Vi)/reagent (SiH) molar ratio of from more than 0.5 to 1.5, preferably of from more than 1 to 1.2, and that, at any moment in the hydrosilylation reaction, the amount of reagent (SiH) present, expressed as mass of SiH functions (29 g per 1 function), corresponds to less than 2%, preferably less than 1% of the reaction mass, excluding the mass of solvent. In the definition of a mole of hydrogenoheptamethyltrisiloxane, reagent (SiH), the xe2x80x94SiH function is considered as being the elemental species. In the definition of a mole of styrene, reagent (Vi), a gram-molecule of styrene is considered as being the elemental species. Karstedt hydrosilylation catalyst is used, for example, in a proportion of from 1 to 300 parts, preferably from 5 to 100 parts, by mass of platinum per million parts by mass of reagents (SiH) and (Vi) used. The hydrosilylation operation is preferably carried out under atmospheric pressure. The introduction of the reagents (SiH) and (Vi) is preferably carried out by simultaneously adding the two reagents continuously to the reaction mass comprising the solvent and the catalyst. The duration of the additions is adjusted such that the reagent (Vi) is consumed by hydrosilylation as it is introduced. The solvent and the unreacted reagents are then removed. Their removal can be carried out by distillation under vacuum or under reduced pressure (for example about 1.013 Pa to 101,300 Pa). This distillation operation is followed by a hydrogenation operation. This can be carried out at a temperature from about 25 to 200xc2x0 C., preferably from about 50 to 150xc2x0 C., at a hydrogen pressure from about 0 to 50 bar, preferably from about 5 to 25 bar, in the presence of a hydrogenation catalyst such as platinum or palladium, in an amount of from 0.01 to 5%, preferably from 0.01 to 1%, by weight of metal relative to the mass to be hydrogenated. The medium is then optionally subjected to an operation to remove the products other than the heptamethyltrisiloxanes containing polarizable functions. This removal operation can be carried out by distillation under vacuum or reduced pressure, for example a pressure from about 1.013 Pa to 101,300 Pa.
The fragrance composition which forms the subject of the invention can comprise from about
3 to 20% of its weight of a fragrance base, and
75 to 97% of its weight of a lipophilic solubilizing agent based on at least one of the polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2).
The fragrance base present can be any compound used in the perfume industry and responsible for various perfume notes. A distinction is made among hesperidic fresh notes, eaux de cologne and fresh waters; among floral notes, simple, flowery, green flowery and aldehydic flowery types; among fern notes, amber or aromatic fern; among oriental notes, spiced oriental and flowery amber types; among chyphre notes, fruity chyphre, aldehydic flowery chyphre, green chyphre and leathery chyphre types.
As examples of chemical compounds which can form part of the composition of the said fragrance base, mention may be made, in a non-limiting manner, of acetophenone, methylacetophenone, cinnamic aldehyde, amylcinnamic aldehyde, lanlsic aldehyde, cuminic aldehyde, cyclamen aldehyde, hydratropic aldehyde, p-cresyl methyl ether, benzophenone, citral, citronellyl oxyacetaldehyde, allyl hexanoate, amyl hexanoate, cinnamyl isobutyrate, geranyl acetate or phenyl acetate, linalyl acetate, menthyl acetate, phenylethyl acetate, vetiveryl acetate, jasmyl acetate, phenylethyl formate, ethylmethylphenyl glycidate, eugenol, isoeugenol, geraniol, citronellal, hydroxycitronellal, ionone, methylionone, phenylacetaldehyde dimethyl acetal, menthol, musk, phenylethyl alcohol, pinene derivatives, camphene derivatives, carvone, cinnamyl alcohol, coumarin, dimethylbenzylcarbinyl acetate, heliotropin, isocyclocitral, methylnonyl acetaldehyde, undecalactone, vanillin, etc. taken together or as mixtures with each other.
The fragrance composition forming the subject of the invention is a solution.
The solubilizing agent present can consist of at least one of the polyorganosiloxanes, in particular organodisiloxanes and organotrisiloxanes, containing a polar or polarizable function of formula (I) or (Ixe2x80x2).
According to one embodiment, the said solubilizing agent consists of at least one of the polyorganosiloxanes, in particular organodisiloxanes and organotrisiloxanes, containing a polar or polarizable function of formula (I) or (Ixe2x80x2), combined with at least one other volatile or non-volatile solvent for fragrance bases, such as volatile silicones (for example hexamethyldisiloxane, decamethylcyclopentasiloxane, linear volatile polydimethylsiloxanes, linear or cyclic volatile alkylpolymethylsiloxanes in which the alkyl radical contains from 2 to 13 carbon atoms, described in U.S. Pat. No. 5,160 494, ethanol, propylene glycol and esters (for example diethylene glycol dioctanoate or diisononanoate).
The said other solvent(s) can be present in a polyorganosiloxane(s) containing a polar or polarizable function of formula (I) or (Ixe2x80x2)/other solvent(s) weight ratio from about 5/95 to 95/5, preferably from about 10/90 to 90/10, most particularly from about 25/75 to 90/10.
Most preferably, the said solubilizing agent consists:
of phenylethylheptamethyltrisiloxane (PEHMTS) or
of a mixture (M) consisting
for more than 70% by mass, generally for at least 75% by mass, of phenylethylheptamethyltrisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z1)xe2x80x94Oxe2x80x94SiMe3,
in which Z1 represents the xe2x80x94CH2xe2x80x94CH2xe2x80x94Ph function
for less than 25% by mass, generally from 10 to 20% by mass, of trisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z2)xe2x80x94Oxe2x80x94SiMe3,
in which Z2 represents the xe2x80x94CH(CH3)xe2x80x94Ph function
and less than 5% by mass, generally from 0 to 2% by mass, of trisiloxane of formula
Me3Sixe2x80x94Oxe2x80x94Si(Me)(Z3)xe2x80x94Oxe2x80x94SiMe3,
in which Z3 represents the xe2x80x94CHxe2x95x90CHxe2x80x94Ph function
in which formulae Me represents a methyl radical and Ph represents a phenyl radical,
the said phenylethylheptamethyltrisiloxane or the said mixture (M) possibly being alone or combined with a volatile silicone solvent, in particular hexamethyldisiloxane, and/or ethanol, in a (PEHMTS)/hexamethyldisiloxane and/or ethanol, or mixture (M)/hexamethyldisiloxane and/or ethanol, weight ratio from about 5/95 to 95/5, preferably from about 10/90 to 90/10, most particularly from about 25/75 to 90/10.
This combination makes it possible to prepare fragrance compositions from fragrance bases of very diverse polarities, in particular as diverse as those of coumarin, vanillin, acetophenone and lavender, these fragrance bases having the following Hansen solubility parameters:
The polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2) also give the fragrance composition forming the subject of the invention sensory properties (in particular a dry feel without residue).
The fragrance composition forming the subject of the invention can also comprise up to 5% of its weight of other constituents, such as preserving agents, light-stabilizers, oxygen-stabilizers, dyes, refreshing agents such as menthyl lactate and menthone glycerol acetal, moisturizers, preserving agents, etc.
The fragrance composition forming the subject of the invention is present in the form of a solution; it can be used as an alcohol-free fragrance or a fragrance containing a small amount of alcohol (as it is or on a textile support or the like) or as an additive for fragrancing cosmetic formulations (care creams, deodorants, antiperspirants, shaving products, etc.).
A second subject of the invention consists of the use, in fragrance compositions comprising a fragrance base, of polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2) as agents for dissolving the said fragrance base.
The present invention is also directed towards the use, in fragrance compositions comprising a fragrance base, of polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2) as emollients (providing sensory properties).
A third subject of the invention consists of a process for preparing a liquid fragrance composition containing a fragrance base, by dissolving the said fragrance base using at least one of the polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2).
The present invention is also directed towards a process for giving sensory properties to a liquid fragrance composition containing a fragrance base, by dissolving the said fragrance base using at least one of the polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2).
The polyorganosiloxanes containing a polar or polarizable function of formula (I) or (Ixe2x80x2) which are preferred, the amounts of the said polyorganosiloxanes used, and those of the fragrance base and of the other solvents or additives optionally present, have already been mentioned above.
The examples which follow are given without any limitation being implied.